Treatment of hydrocarbons



TREATMENT OF HYDROCARBONS Filed OCb. 10, 1942 iba-arbe?" Patented Jan. 15, 1946 UNITED STATES PATENT "OFFICE 2,392,896 reimriviiz's'r or nroitocliiisons Samuel S. Allende'i'-, New York, fN. Y., assgn'or :to

Universal Oil Products Company, Chioago,:Ill,-,

a corporation of Delaware Application Voctober 10, 1942, seriali No. 'raises s craims. (o1. acoge-83.15)

This -is a continuation-impart of my co-pending application Serial No. 320,829, led February l in ordinary gasoline, that is, a certain percentage of them is essentialforpsuicient vapor pressure to insure ea-se in starting, while an excess tends to produce vapor lock. For these reasons the total percentage of iV-carbon atom hydrocarbons is commonly adjusted in conjunction with the boiling range and vapor pressure of the other gasoline components to produce a gasoline of desirable starting characteristic according to seasonal demands. Since the amount of butane required for this purpose `is less 'in summer than in Winter there are frequent periods of over production of these gaseous hydrocarbons during which they are utilized largely for domestic and .industrial fuel purposes. Therefore, it is of considerable importance at the present time to convert as much as possible of V'the excess butane production `into gasoline, and the present invention is especially concerned with a process for accomplishing this object. y

Inv onespecic embodiment the present 'invention comprises a process for producing gasoline from saturated gaseous hydrocarbons occurring in natural and casing head gases which comprises fractionally distilling a mixture of absorption oil, dissolved hydrocarbons, and oleiin polymers formed in the process to separate a fraction consisting of gasoline and lighter hydrocarbons from a lmixture of absorption oil andv relatively high boiling polymers, distilling said fraction to separate gasoline from normally gaseous hydrocarbons, fractionally distilling and depropanizing said gaseous hydrocarbons to separate Ca and lighter hydrocarbons from a butane fraction, subjecting said butane' fraction to cracking to form .and butane cracking treatment.

In another specific embodiment the present invention comprises a process for producing valuable olefinic vprod'l'lcts from saturated gaseous hydrocarbons occurring I in natural`l and ca-'sing head .gases `which comprises fractionally -distilljiivl'g a mixture 'o'ffabfsorption oil, dissolved hydrocarbons, and olenic polymers formed irllvtlle,process to separate a fraction consisting of 'gasolinefand lighter hydrocarbons vfrom 'a `mixture 'of iaslo'oiption on and relatively highbpiiing polymers, uistilli'rlg `said fractionto separate gasoline yfrom the normally gaseous-hydrocarbons, fractiona y fdistilling and ,'depropanining 'saidjgaseous vhydrocarbons 'to separate C3 and `lighter hydrocarbons from the butane fraction, subjecting' 'said butano fraction to erakmg to' forni a product consisting 'of van olefin-'containing 'gas and olenic polymers, subjecting said product to ydistillation to 'separate it l'l'to fractions containing 'C2 Silldst'alitial por'- tions or whichare oiejriic and lighter gases, gases containing a substantial portion o`f ole'fins -of higher molecular vseight and a heavier fraction containing oleiinic polymers, returning 'the latter to the first fractional distillation step and separately recovering the gases containing a substantialportionof olelns ofhigh'er molecular Weight and the fraction containing C2 substantial portions Y'of which are olinic and lighter gases'.

The process of thisinvention yields a hydrocarbon material of khigh Octane number useful as blending ld t0 increase the antikrl'ock value of fuels inferior in this respect. This invention involves the production of polymeriaable -olens by butano ackingoi pyiolysis followed by Cataiytie polymerization to normally squid .products and return of said polymer products to fractional distillation-n the 'stripping and distilling columns employed also fdr -separatingV butanes and higher hydrocarbons from lthe-alos()rptorl' Oil-l The process of this invention -Inafy also'beelnployed for the production of leflnic material whichl ismuch in demand forus'e in alkylation processes and for processes for the production of butadiene `and other materials for manufacturing synthetic rubber; For example butenes may be dehydrogenated to produce bu adiene and ethylene may be employed to-alltyla e benzene for the vproduction 'of ethylben'zeiieV from which styrene may be produced, Also the' olens produced may be employedrin various wavll'iylationprocesses for the production of 'blending materials desirable for use in aviation motor iuels tubma'r reactorrornheater designeatnatin y thetime dui-ing 'which butane is cracked Lthere tain amounts of normally liquid aromatic and oleonic hydrocarbons commonly referred to as pyrolytic polymers which may be utilized as aband the relatively high boiling polymers may be used as absorption oil for separating butanes from' lowerboiling gases. i c i g Sulfuric acid is another material which may be used as catalyst in the polymerization oi nor- "mally gaseous oleflns, particularly butenes, to produce high yields of normally liquid polymers sorption oil in the separation oi C2 and lighterhyi drocarbons from C3 and higher olefin-containing hydrocarbons, the latter utilizable as charging stock for polymerization, alkylation; etc. l

Polymerization of gaseous olens Yformed Vby cracking of butane may be effected ata temperature inthe approximate range of Z50-5509 F. under a pressure of the order of 200-1500 pounds persquare inch in the presenceof'so-called solid phosphoric acid catalysts, as described in United States Patent No. 1,993,513 and others. This solid phosphoric acid catalyst may be made by the successive steps of (l) mixing the phosphoric acid with affinely divided and relatively inert, generally siliceous, carrying material, such as, for example, diatomaceous earth to form a'ratherwet paste (the acid ordinarily being in major proportion by weight); (2) calcining at a temperature of the order orfr6l009329 F., to produce a solid cake; (3) grinding and sizing to produce particles ofusable mesh; and (4) rehydrating the catalyst granules at a temperature of the order of 450- 550 F.junder substantially atmospheric pressure -to produce an acid composition corresponding to optimum polymerizing activity. This procedure may be varied by forming particles from the original paste by extrusion or pelleting methods and following with the calcining and rehydrating steps. In the reactions taking place during calcining it is evident that some of the acid is xed" on vthe carrier and that some metaphosphoric acid, which is substantially without polymerizing activity,` is formed. The Vrehydrating step evi- Identlyproduces an acid composition corresponding closely'to the pyro-acid having a formula `HiPzOfz and corresponding to the double oxide 2f01mulaP2O52H2O.

The solidphosphoric acid Ycatalysts preferred --for useinfthe present invention are characterized iby the fact that they are precalcined before use both' to iixthecomposition of the acid and to form particles of a granular structure capable of withstanding the conditions of service to which theyare subjected. When these catalysts become coatedwith. carbonaceous deposits they can be reactivated by oxidation Vwith ainfor with gas mixitures ,ofl controlled oxygen concentration at temperatures of the approximate order of 800-1000 F.,followed by contacting with superheated steam `at about 450-5501 F., under atmospheric pressure vto rehydrate the l'acid to the most desirable composition. lRehydration at higher temperatures may be` made under steam pressure corresponding `to approximately the water vapor pressureof the .catalyst'at' the operating temperature.

lPolymerization of the olefin content of such gases as are produced by the pyrolysis of Abutane maybe effected by passing the gases through a Ureactor containing a section or several sections of the solid catalyst at a rate consistent with the production of a good yield of liquid products.

-Following the polymerizationstep, the total prodjuctsmay befractionated to separate a stabilized gasoline from unccnverted gases and relatively highboilingfliquid products: yThe gaseous products maybe Asubjectedtovfurthercracking Vto produce additional quantities of gaseous' olens hydrogenatable tok paraffin fractions of high octane number. This type of polymerization is eiiected conveniently by contacting, the butene- "containing fraction with sulfuric acid of (S-'70% concentration at va temperature in the approximate 'range of 10D-200 F. under a pressure of the order of 15G-600 pounds per square inch. Under these conditions 4carbon atom hydrocar bon fractions containingboth isobutene and nor-f mal butenes yield interpolymers offrelatively Yhigh octane number. Polymers of isobutenemaybe produced from the same charging stock bycontacting it vwith Gti-'70% sulfuric acid at approximately l5-100 F. toabsorb isobutene inthe sulfuric acid followed by heating the sulfuric acid and absorbed isobutene to approximately 200 F. to effect formation of polymers.

For the purpose of illustrating the combination of steps characteristic of one form of lthe' present invention the attached `drawing'shows diagrammatically a typical process flow'for'producing gasoline from saturated gaseous hydrocarbons absorbed from natural or casing head gases. e Y e Referring to the drawing, a rich oil` froi'n a natural gasoline plant absorber containingvdissolved hydrocarbonsmay be introducedthrfough line l to stripping zone 2 which may comprise a fractional distilling column of adequatevdesign by which dissolved hydrocarbons may be separated from the higher boiling material utilized as absorption oil. v

The lean absorption oil may be returned through line 3 to the absorbing lplan t,not shown, while the gaseous and liquid hydrocarbonsseparated therefrom in stripping zone 2 may be withdrawn through line 4 to stabilizing zone 5 which may comprise a fractional distillingfcolumn from which gaseous hydrocarbons may be separated from normallylquidproducts of gasoline boiling range. Said liquid products Vmay be withdrawn from stabilizing zone 5 through'line 6 to storage, while the gaseous hydrocarbons-may be conducted through line l to depropanizing zone 8 which may comprise fractionalrdistillation equipment of adequate design for separating' C3 and lighter gases from a substantially butano fraction. The C3 and lighter gases may bedischarged from depropanizing zonet through` line 9 for use as fuel or for another purpose. Y The butane fraction may be withdrawn from depropanizing zone Sand passedthrough line IG to cracking zone Il which` may comprise a tubular reactor or plurality ,of such reactors maintained at a temperature in the approximate range of 900-1200? VF. to yieldaproductcontaining butenes, unconverted butano. lower boiling paraffin and olefin gases and some normally liquid materials generally containing clefinic and aromatic hydrocarbonsand commonly classed as pyrolytic polymers.. vFrom cracking zone IVI the cracked products may be passed by way vof line I2 to de-ethanizingrzone i3 for separating TC2 and lighter gases. De-ethanizingzone i3-may comprise absorbing and Stcljippng` QllmmS in which pyrolytic polymerspniaybe utilized` as absorbent for butanesjand butenes. The C3' and lighter gases remaining unabsrbdfin `dethan zing zone I3 may be conducted thence through lines I4 and 9 to be used as fuel or all or a portion thereof may be conducted through line 23 to processes in which ethylene may be desirable as a charging material.

From de-ethanizing zone I3 the pyrolytic polymers containing absorbed hydrocarbons may be conducted through line I5 to separating zone I6 which may comprise a fractional distilling co1- umn by which C3 and heavier olens and parafiins may be separated and conducted thence through line I1 to polymerizing zone I8, While the normally liquid products comprising essentially pyrolytic polymers may be recycled through line I 9 to line I to commingle with the absorption oil containing dissolved parainic hydrocarbons being charged through line I already mentioned. A portion of the material being conducted through line I9 may be discharged therefrom through line 20 to de-ethanizing zone I3 for further absorption use therein.

Polymerizng zone I8 may comprise a reactor or plurality of reactors containing a granular calcined composite of an acid of phosphorus and a siliceous absorbent operated under conditions of temperature and pressure adequate to effect formation of liquid polymers from normally gaseous olens. The products from polymerizing zone I8 may be discharged therefrom through line 2l and therein conducted to line 4, already mentioned, through which incoming gaseous and liquid hydrocarbons may be introduced to stabilizing zone 5 in which liquid hydrocarbons contained in the original charge and those produced by thermal and catalytic polymerization may be separated as a gasoline fraction Which may be withdrawn through line 6 to storage as hereinabove indicated.

When desired all or a portion of the material passing through line I1 may be conducted through line 22 to other processes in which it may be utilizable.

The following specific example is presented as illustrative of one form of the process as it may be conducted using a process flow as hereinabove described. A hydrocarbon fraction containing approximately 30 mole per cent isobutane and '70 mole per cent n-butane obtained from natural gas by absorption, stripping, and distillation treatments may give a gasoline yield of 350 barrels, comprising approximately 100 barrels of pyrolytic polymer and 250 barrels of catalytic polymer based upon 1000 barrels of butane charged. Such typical operation may comprise cracking the butane fraction at 1000 F. under a pressure of 750 pounds per square inch to produce an olen-containing gas and pyrolytic polymers, followed by contacting such olefin-containing gas at 475 F. under a pressure of 1000 pounds per square inch with a calcined composite of pyrophosphoric acid and diatomaceous earth to produce normally liquid polymers. A mixture of pyrolytic and catalytic polymers from the process of this invention may be blended, as hereinabove indicated, `v with the natural gasoline recovered from the natural or casing head gases to produce a motor fuel of high octane number.

The foregoing description of the invention and the illustrative example serve to define its character and utility, but the exact details set forth are not to be construed as imposing undue limitations upon the generally broad scope of the invention.

I claim as my invention:

1. In the recovery of butanes from natural and casing head gases by absorption thereof in an absorber oil, the method of producing more valuable products from the recovered butanes which comprises combining with the enriched absorber oil normally liquid polymers formed as hereinafter set forth, vaporizing from the resultant mixture gasoline boiling hydrocarbons and absorbed gases, commingling with the resultant vapor-gas mixture polymerization products formed as hereinafter set forth, fractionating the mixture thus formed to separate therefrom a gasoline distillate and a butane fraction, recovering said distillate, cracking said butane fraction to form oleiinic gas and normally liquid polymers, combining at least a portion of the latter with said enriched absorber oil as aforesaid, subjecting the olenic gas to catalytic polymerization and commingling the resultant products With said vapor-gas mixture as aforesaid.

2. In the recovery of butanes from natural and casing head gases by absorption thereof in an absorber oil, the method of producing more valuable products from the recovered butanes which comprises combining with the enriched absorber oil normally liquid polymers formed as hereinafter set forth, vaporizing from the resultant mixture gasoline boiling hydrocarbons and absorbed gases, commingling with the resultant vapor-gas mixture polymerization products formed as hereinafter set forth, fractionating the mixture thus formed to separate therefrom a gasoline distillate and a butane fraction, recovering said distillate, cracking said butane fraction at a temperature of from about 900 to about 1200 F. and under a pressure of from about 200 to about 1000 pounds per square inch to form olenic gas and normally liquid polymers, combining at least a portion of the latter with said enriched absorber oil as aforesaid, subjecting the oleinic gas to catalytic polymerization and commingling the resultant products with said vapor-gas mixture as aforesaid.

3..'I'he process set forth in claim 1 further characterized in that the olefinic gas is subjected to polymerization in the presence of a catalyst comprising phosphoric acid.

Y 4. The process set forth in claim 1 further characterized in that the olefnic gas is subjected to polymerization in the presence of a catalyst comprising sulfuric acid.

5. In the recovery of butane from absorber oil enriched with natural or casing head gases, the, method of producing more valuable products from the recovered butane which comprises stripping the enriched absorber oil of its butane and gasoline boiling range hydrocarbon content, separating a butane fraction from the products of the stripping step, subjecting said butane fraction to a thermal conversion treatment to form liquid polymer and olenic gases, separating the liquid polymer from the olenic gases, combining said liquid polymer with the enriched absorber oil for treatment in said stripping step, subjecting the olenic gases to catalytic conversion to form a liquid product boiling in the range of gasoline, and combining the products from the last mentioned conversion step with the products of the stripping step for treatment in said separating step.

SAMUEL S. ALLENDER. 

